Conveniently prepared naphthalene and perylene derivatives as building blocks for organic electronic materials and dyestuff

ABSTRACT

The present invention provides the compounds of formulae (3) and (1), wherein n is 0 or 1, R 11  and R 12  are the same and are selected from the group consisting of CN, OR 300 , Si(R 301 ) 3 , NHR 302 , NR 303 R 304 , SR 305  and R 306 , or R 11  and R 12  together are selected from the group consisting of (a), (b), and (c) and X is Cl, Br or I, and a process for the preparation of compounds of formula (3) comprising the compounds of formula (1) as key intermediates.

The invention relates to naphthalene and perylene derivatives.

Many naphthalene and perylene derivates are important colorants. Beside this traditional application, naphthalene and, in particular, perylene derivatives gain more and more interest in other applications such as in organic field-effect transistors, organic light emitting devices, photovoltaic devices such as dye-sensitized solar cells (DSCs), and xerography.

The design and preparation of naphthalene and perylene derivatives, which are tuned to be suitable for a particular application, are an active area of research.

Naphthalene and perylene derivatives, which are substituted in all four peri-positions, in particular with substituents such as cyano, alkyoxy, aryloxy, silyl, substituted amino, alkylthio, arylthio, alkyl and aryl, could be suitable for many applications.

DE 340091 describes the preparation of 3,4,9,10-tetracyanoperylene from 3,4,9-tricyano-10-bromoperylene. 3,4,9-tricyano-10-bromoperylene was prepared from 3,4,9,10-tetrabromo-perylene, which was obtained by bromination of perylene in nitrobenzene.

JP 2002-012861 describes perylene derivatives, which carry a substituted or unsubstituted amino group in the 1 or 2 position. In particular, JP 2002-012861 describes the preparation of 3,4,9,10-tetraphenylperylene and 3,4,9,10-tetracyanoperylene, both substituted in 1 and 7 position with a substituted amino group, from 1,7-dibromo-3,4,9,10-tetraphenylperylene, respectively, 1,7-dibromoperylene 3,4,9,10-tetracarbonitrile.

Zinke, A.; Pongratz, A., Funke, K. Chem. Ber. 1925, 58, 330 to 332 and DE 498 039 describes a process for the halogenation of perylene, wherein the halogenation is effected in the presence of a solvent such as nitrobenzene, and the halogen is employed in statu nascendi. According to the examples 3,9-dichloroperylene, tetrachloroperylene (mp. 350° C.), and hexachloroperylene (mp. 356° C.) are prepared by running an acetic acid solution of hydrogen peroxide into a solution of perylene in nitrobenzene at the same time as an acetic acid solution of concentrated hydrochloric acid is being added. It is said that the tetrachloroperylene is likely to be the 3,4,9,10-tetrachloroperylene. A further substitution of X is not described.

Many naphthalene derivatives, which are chlorinated or brominated in all four pen-positions, are known (DE 66611, Whitehurst, J. S. J. Chem. Soc. 1951, 221 to 226, Bassilios, H. F.; Salem, A. Y.; Shawky, M. Rec. Trav. Chim Pays-Bas 1962, 81, 209 to 214, DE 1958 595, Mesh, L. A.; Grudtsyn, Y. V. J. Org. Chem. USSR 1977, 13, 2384 to 2389, Brady, J. H.; Redhouse, A. D.; Wakefield, B. J. J. Chem. Res. Miniprint 1982, 6, 1541 to 1554, Otsubo, T.; Sukenobe, N.; Aso, Y.; Ogura, F. Chem. Lett. 1987, 315 to 316, Garcia, R.; Riera, J.; Carilla, J.; Julia, L.; Molins, E., Miravitlles C. J. Org. Chem. 1992, 57, 5712, Kodama, T.; Kodani, M.; Takimiya, K.; Aso, Y.; Otsubo, T. Heteroatom. Chem. 2001, 12, 287 to 292).

DE 1 154 799 describes the following process

DE 1 154 799 emphasizes that it was not possible to obtain the tetrahalogenated naphthaline. A further substitution of X is not described.

It was the object of the present invention to provide naphthalene and perylene derivatives, which are substituted in all four peri-positions.

The object is solved by the process of claim 1, the compounds of claim 8 and the compounds of claim 12.

The process of the present invention for the preparation of compounds of formula

wherein

n is 0 or 1, R ¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰, Si(R³⁰¹)₃, NHR³⁰², NR³⁰³R³⁰⁴, SR₃₀₅ and R³⁰⁶

-   -   wherein     -   R³⁰⁰, R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵ and R³⁰⁶ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be             substituted with one or more substituents selected from the             group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³             and         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷,             -   wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶                 and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹¹ and R¹² together are selected from the group consisting of

-   -   wherein     -   L¹ and L² are C₁₋₆-alkylene, C₆₋₁₄-arylene, or         C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene,     -   R²⁵ is H, C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,         C₅₋₈-cycloalkyl, or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰¹⁰R³⁰¹¹, O—R³⁰¹² and S—R³⁰¹³, and         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰¹⁴R³⁰¹⁵, O—R³⁰¹⁶ and S—R³⁰¹⁷,             -   wherein R³⁰¹⁰, R³⁰¹¹, R³⁰¹², R³⁰¹³, R³⁰¹⁴, R³⁰¹⁵, R³⁰¹⁶                 and R³⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,     -   L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or         C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene, and

R¹⁵, R¹⁶, R¹⁷, R¹⁹, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴,

-   -   wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,     -   wherein     -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl         may be substituted with one or more substituents selected from         the group consisting of phenyl, NR³⁰²⁰R³⁰²¹, O—R₃₀₂₂, S—R³⁰²³,         NO₂, CN and halogen,     -   C₆₋₁₄-aryl may be substituted with one or more substituents         selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰²⁴R³⁰²⁵,         O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen,         -   wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and             R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl or             phenyl,             or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

comprises the step of treating a compound of formula

wherein

n has the meaning as depicted for formula (3),

R⁹ and R¹⁰ are the same or different and are COOH or COOR²⁰⁰,

-   -   wherein R₂₀₀ is C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,         C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR²⁰⁰⁰R²⁰⁰¹, O—R²⁰⁰² and S—R²⁰⁰³,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR²⁰⁰⁴R²⁰⁰⁵, O—R²⁰⁰⁶ and S—R²⁰⁰⁷,         -   wherein R²⁰⁰⁰, R²⁰⁰¹, R²⁰⁰² and R²⁰⁰³, R²⁰⁰⁴, R²⁰⁰⁵, R²⁰⁰⁶             and R²⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl or             phenyl             or

R⁹ and R¹⁰ together are

and

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R²⁰⁰, OR²⁰¹, SR²⁰², OC(O)R²⁰³ and C(O)OR²⁰⁴,

-   -   wherein R²⁰⁰, R²⁰¹, R²⁰², R²⁰³ and R²⁰⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen, wherein             R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷             are the same or different and are C₁₋₁₀-alkyl or phenyl,             or

R³ and R⁵, respectively, R⁴ and R⁶ together are

-   a) with MOH, wherein M is an alkali metal, N(R⁴⁰⁰R⁴⁰¹R⁴⁰²R⁴⁰³),     P(R⁴⁰⁰R⁴⁰¹R⁴⁰²R⁴⁰³) or hexa(C₁₋₁₀-alkyl)guanidinium,     -   wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰² and R⁴⁰³ are the same or different and         are selected from the group consisting of H, C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl and C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with phenyl,         -   C₆₋₁₄-aryl may be substituted with C₁₋₁₀-alkyl,             and

b) an X-donor, wherein X is Cl, Br or I,

in order to obtain a compound of formula

wherein

X has the meaning as depicted for the X-donor,

n has the meaning as depicted for formula (3),

and

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the meaning as depicted for formula (2).

C₁₋₁₀-alkyl and C₁₋₂₀-alkyl can be branched or unbranched. Examples of C₁₋₁₀-alkyl are methyl, ethyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 1,1-dimethyl-3,3-dimethylbutyl, nonyl and decyl. Examples of C₁₋₂₀-alkyl are C₁₋₁₀-alkyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl,

C₂₋₂₀-alkenyl can be branched or unbranched. Examples of C₂₋₂₀-alkenyl are vinyl, propenyl, cis-2-butenyl, trans-2-butenyl, 3-butenyl, cis-2-pentenyl, trans-2-pentenyl, cis-3-pentenyl, trans-3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl, linoleyl (C₁₈), linolenyl (C₁₈), oleyl (C₁₈) and arachidonyl (C₂₀).

C₂₋₂₀-alkynyl can be branched or unbranched. Examples of C₂₋₂₀-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl and icosynyl (C₂₀).

Examples of C₅₋₈-cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Examples of C₆₋₁₄-aryl are phenyl and naphthyl.

Examples of halogen are F, Cl, Br and I.

Examples of alkali metals are Na, K and Li.

Examples of N(R⁴⁰⁰R⁴⁰¹R⁴⁰²R⁴⁰³) are tetra (n-butyl)ammonium and decyl-methyl-dioctyl-ammonium.

Examples of hexa(C₁₋₁₀-alkyl)-guanidinium are hexamethylguanidinium and hexaethylguanidinium.

Examples of X-donors are X—X, X-succinimide and N,N″-di-X-isocyanuric acid.

Preferably, R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃,

-   -   wherein     -   R³⁰⁰ and R³⁰¹ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or         C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be             substituted with one or more substituents selected from the             group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³             and         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷,             -   wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶                 and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹¹ and R¹² together are

-   -   wherein     -   L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or         C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene.

More preferably, R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃,

-   -   wherein     -   R³⁰⁰ and R³⁰¹ are C₁₋₂₀-alkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl may be substituted with one or more substituents             selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹,             O—R³⁰⁰² and S—R³⁰⁰³ and         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷,             -   wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶                 and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹¹ and R¹² together are

Most preferably, R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃,

-   -   wherein     -   R³⁰⁰ and R³⁰¹ are C₁₋₂₀-alkyl or C₆₋₁₄-aryl,         -   wherein         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷,             -   wherein R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or                 different and are C₁₋₁₀-alkyl or phenyl,                 or

R¹¹ and R¹² together are

Preferably, n is 1,

Preferably, R¹⁵, R¹⁶, R¹⁷, R¹⁹, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, Cl, Br, I, CN and OR³¹¹,

-   -   wherein R³¹¹ is C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,         C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen,     -   C₆₋₁₄-aryl may be substituted with one or more substituents         selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰²⁴R³⁰²⁵,         O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen,         -   wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and             R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl or             phenyl,             or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

Preferably, if n is 0, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are H.

Preferably, if n is 1, R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰, are the same or different and are selected from the group consisting of F, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴,

-   -   wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen,             -   wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶                 and R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

More preferably, if n is 1, R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰ are the same or different and are selected from the group consisting of Cl, Br, I, CN and OR³¹¹,

-   -   wherein R³¹¹ is C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,         C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen,             -   wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶                 and R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

Most preferably, if n is 1, R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰ are the same or different and are selected from the group consisting of Cl, Br, I and CN.

Even most preferably, if n is 1, R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰ are Cl.

Preferably, R⁹ and R¹⁰ are the same and are COOH,

or

R⁹ and R¹⁰ together are

More preferably, R⁹ and R¹⁰ together are

Preferably, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, Cl, Br, I, CN and OR²⁰¹,

-   -   wherein R²⁰¹ is C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,         C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen,             -   wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶                 and R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R³ and R⁵, respectively, R⁴ and R⁶ together are

Preferably, if n is 0, R¹, R², R³ and R⁴ are H.

Preferably, if n=1, R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶, are the same or different and are selected from the group consisting of F, Cl, Br, I, CN, R²⁰⁰, OR²⁰¹, SR²⁰², OC(O)R²⁰³, and C(O)OR²⁶⁴,

-   -   wherein R²⁰⁰, R²⁰¹, R²⁰², R²⁰³ and R²⁰⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen,             -   wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶                 and R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R³ and R⁵, respectively, R⁴ and R⁶ together are

More preferably, if n is 1, R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ are the same or different and are selected from the group consisting of Cl, Br, I, CN and OR²⁰¹,

-   -   wherein R²⁰¹ is C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,         C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen,             -   wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶                 and R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R³ and R⁵, respectively, R⁴ and R⁶ together are

Most preferably, if n is 1, R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ are the same or different and are selected from the group consisting of Cl, Br and OR²⁶¹,

-   -   wherein R²⁰¹ is C₆₋₁₄-aryl,         -   wherein         -   C₆₋₁₄-aryl may be substituted with C₁₋₁₀-alkyl,             or

R³ and R⁵, respectively, R⁴ and R⁶ together are

Preferably, M is an alkali metal, more preferably Na.

Preferably, X is Cl or Br, more preferably Br.

Preferably, the compound of formula (2) is first treated with MOH, followed by treatment with the X-donor. Usually the process is performed without the isolation of any intermediate products in a so-called “one pot reaction”.

The compound of formula (2) is commercially available or can be obtained by methods known in the art.

Preferably, the X-donor is X—X. More preferably, the X-donor is X—X, wherein X is Cl or Br. Most preferably, the X-donor is X—X, wherein X is Br.

Preferably, the treatment with MOH and the treatment with the X-donor are performed in an aqueous solvent such as water or mixtures of water with a suitable organic solvent such as tetrahydrofuran or dioxane. More preferably, the treatment with MOH and the treatment with the X-donor are performed in water as solvent.

Preferably, the treatment with MOH is performed at a temperature from 10 to 100° C., more preferably from 20 to 60° C.

Preferably, the molar ratio of MOH/compound of general formula (2) is 4/1 to 20/1, more preferably 4/1 to 10/1, most preferably 4/1 to 7/1.

Preferably, the molar ratio of the X-donor/compound of general formula (2) is 4/1 to 30/1, more preferably 4/1 to 20/1, most preferably 4/1 to 17/1.

Preferably, the treatment with the X-donor is performed at a temperature from 10 to 260° C., more preferably from 20 to 120° C., most preferably from 20 to 100° C.

The compound of formula (1) can be isolated by methods known in the art, for example by extraction with a suitable organic solvent such as dichloromethane. After isolation the compound of formula (1) may be further purified by methods known in the art, such as recrystallization or chromatography.

The compounds of formula (3) can be directly obtained from the compounds of formula (1) or via intermediate compounds in a multiple steps by methods known in the art.

For example, the compounds of formula (3), wherein R¹¹ and R¹² are both CN or OR³⁰⁰, can be prepared by treating the compound of formula (1) with M²CN or M²0R³⁰⁰ , wherein M² can be an alkali metal or a transition metal.

For example, the compounds of formula (3), wherein R¹¹ and R¹² both are Si(R³⁰¹)₃, can be prepared by treating the compound of formula (1) with an organyl-M³, wherein M³ can be an alkali metal, followed by, X²—Si(R³⁰¹)₃, wherein X² can be halogen.

For example, the compounds of formula (3), wherein R¹¹ and R¹² together are

can be prepared by treating the compound of formula (1) with sulphur.

For example, the compounds of formula (3), wherein R¹¹ and R¹² both are NHR³⁰², NR³⁰³R³⁰⁴, respectively, SR³⁰⁵ can be prepared by treating the compound of formula (1) with NH₂R³⁰², NHR³⁰³R³⁰⁴, respectively, HSR³⁰⁵.

For example, the compounds of formula (3), wherein R¹¹ and R¹² both are R³⁰⁶ can be prepared by treating the compound of formula (1) with R³⁰⁶boronic acid in the presence of a suitable catalyst such as Pd[P(Ph)₃]₄.

For example, the compounds of formula

can be prepared by treating the compound of formula

with sulfur.

For example the compound of formula

can be prepared by treating the compound of formula

with 4-(2,4,4-trimethylpentan-2-yl)phenol and K₂CO₃.

For example, the compound of formula

can be prepared by treating the compound of formula

with n-butyl lithium and trimethylsilyl chloride.

For example, the compound of formula

can be prepared by treating a compound of formula

with CuCN.

Also part of the present invention are compounds of formula

wherein

X is Cl, Br or I,

n is 0 or 1,

and

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R²⁰⁰, OR²⁰¹, SR²⁰², OC(O)R²⁰³ and C(O)OR²⁶⁴,

-   -   wherein R²⁰⁰, R²⁰¹, R²⁰², R²⁰³ and R²⁰⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen,             -   wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶                 and R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R³ and R⁵, respectively, R⁴ and R⁶ together are

with the proviso

-   that if n is 0 and X is Cl, R¹, R², R³ and R⁴ are not H, Cl, CN,     R₂₀₀ or C(O)OR²⁰⁴, wherein R²⁰⁰ and R²⁰⁴ are C₁₋₂₀-alkyl, -   that if n is 0 and X is Br, R¹, R², R³ and R⁴ are not H, Br or R₂₀₀     , wherein R²⁰⁰ is C₁₋₂₀-alkyl, and -   that if n is 1 and X is Cl or br, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸     are not H.

Preferred are compounds of formula

wherein

X is Cl, Br or I,

n is 1,

and

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R²⁰⁰, OR²⁰¹, SR²⁰², OC(O)R²⁰³ and C(O)OR²⁰⁴,

-   -   wherein R²⁰⁰, R²⁰¹, R²⁰², R²⁰³ and R²⁰⁴ are are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR²⁰¹⁴R^(2015, 0—R) ²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen,             wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and             R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl or             phenyl             or

R³ and R⁵, respectively, R⁴ and R⁶ together are

with the proviso

that if n is 1 and X is Cl or Br, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are not H.

More preferred are compounds of formula

wherein

X is Cl, Br or I,

n is 1,

and

R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶, are the same or different and are selected from the group consisting of F, Cl, Br, I, CN, R²⁰⁰, OR²⁰¹, SR²⁰², OC(O)R²⁰³ and C(O)OR²⁰⁴,

-   -   wherein R²⁰⁰, R²⁰¹, R²⁰², R²⁰³ and R²⁰⁴ are are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen,             -   wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶                 and R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R³ and R⁵, respectively, R⁴ and R⁶ together are

The preferences of n, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and X given above for the process for the preparation of compounds of formula (3), also apply to the compounds of formula (1).

In particular preferred are the following compounds

The compounds of formula (1) are versatile building blocks.

Also part of the present invention are compounds of formula

wherein

n is 0 or 1,

R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰, Si(R³⁰¹)₃, NH R³⁰², NR³⁰³R³⁰⁴, SR₃₀₅ and R³⁰⁶

-   -   wherein     -   R³⁰⁰, R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵ and R³⁰⁶ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be             substituted with one or more substituents selected from the             group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³             and         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷,             -   wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶                 and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹¹ and R¹² together are selected from the group consisting of

-   -   wherein     -   L¹ and L² are C₁₋₆-alkylene, C₆₋₁₄-arylene, or         C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene, R²⁵ is H,         C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or         C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰¹⁰R³⁰¹¹, O—R³⁰¹² and S—R³⁰¹³, and         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰¹⁴R³⁰¹⁵, O—R³⁰¹⁶ and S—R³⁰¹⁷,             -   wherein R³⁰¹⁰, R³⁰¹¹, R³⁰¹², R³⁰¹³, R³⁰¹⁴, R³⁰¹⁵, R³⁰¹⁶                 and R³⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,     -   L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or         C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene,         and

R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴,

-   -   wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen,             -   wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶                 and R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

with the proviso that if

n is 0, R¹¹ and R¹² are both CN, then R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are not all H, and that if

n is 1, R¹¹ and R¹² are both CN or phenyl, and R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are H, then R¹⁷ and R²⁰ are not Br.

Preferred are the compounds of formula

wherein

n is 0 or 1,

R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃,

-   -   wherein     -   R³⁰⁰ and R³⁰¹ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or         C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be             substituted with one or more substituents selected from the             group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³             and         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷,             -   wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶                 and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹¹ and R¹² together are

-   -   wherein     -   L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or         C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene,         and

R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴,

-   -   wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen,             -   wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶                 and R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

with the proviso

that if n is 0, R¹¹ and R¹² are both CN, then R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are not all H,

and

that if n is 1, R¹¹ and R¹² are both CN or phenyl, and R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are H, then R¹⁷ and R²⁰ are not Br.

More preferred are compounds of formula

wherein

n is 1,

R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃,

-   -   wherein     -   R³⁰⁰ and R³⁰¹ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or         C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be             substituted with one or more substituents selected from the             group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³             and         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷,             -   wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶                 and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹¹ and R¹² together are

-   -   wherein     -   L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or         C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene,         and

R¹⁵, R¹⁶, R¹⁷, R¹⁹, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴,

-   -   wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen,         -   wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and             R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl or             phenyl,             or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

with the proviso

that if n is 1, R¹¹ and R¹² are both CN or phenyl, and R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are H, then R¹⁷ and R²⁰ are not Br.

Even more preferred are compounds of formula

wherein

n is 1,

R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃,

-   -   wherein     -   R³⁰⁰ and R³⁰¹ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or         C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be             substituted with one or more substituents selected from the             group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³             and         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷,             -   wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶                 and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹¹ and R¹² together are

-   -   wherein     -   L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or         C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene,         and

R¹⁵, R¹⁶, R²¹ and R²² are H, and R^(17, R) ¹⁸, R¹⁹ and R²⁰, are the same or different and are selected from the group consisting of F, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴,

-   -   wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁸²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen, wherein             R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷             are the same or different and are C₁₋₁₀-alkyl or phenyl,             or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

Most preferred are compounds of formula

wherein

n is 1,

R¹¹ and R¹² together are

and

R¹⁵, R¹⁶, R²¹ and R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰, are the same or different and are selected from the group consisting of F, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴,

-   -   wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are C₁₋₂₀-alkyl,         C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl,         -   wherein         -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and             C₅₋₈-cycloalkyl may be substituted with one or more             substituents selected from the group consisting of phenyl,             NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen,         -   C₆₋₁₄-aryl may be substituted with one or more substituents             selected from the group consisting of C₁₋₁₀-alkyl,             NR³⁹²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen,             -   wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶                 and R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl                 or phenyl,                 or

R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

In particular preferred are following compounds

The compounds of formula (3) can be used in various applications, for example as colorants or dyes, or in electronic devices such in organic field-effect transistors, organic light emitting devices and in photovoltaic devices such as dye-sensitized solar cells (DSCs).

Also part of the invention is the use of the compounds of formula (3) in electronic devices.

Also part of the invention is the use of the compounds of formula (3) as dye.

The process of the present invention is advantageous as it allows the convenient preparation of compounds of formula (3).

The key intermediates of the process of the present invention for the preparation of the compounds of formula (3) are the compounds of formula (1) carrying four X-groups, wherein X is Cl, Br or I, in the peri-positions. The compounds of formula (1) are versatile building blocks, which allow the easy introduction of various substituents in the peri-positions by methods known in the art. In case, the compounds of formula (1) also carry suitable substituents such as Cl in the R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and/or R⁸ positions, these substituents can also be easily replaced with other substituents.

The compounds of formula (1) can be prepared in a very convenient and economic manner from the compounds of formula (2) The compounds of formula (2), especially the compounds of formula (2), wherein R⁹ and R¹⁰ together are

are readily available and of low cost. The compounds of formula (1) are usually obtained in high yields (for example higher than 80%), especially when n is 1, X is Br, and R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ are the same and are selected from the group consisting of H, Cl, and Br, or R³ and R⁵, respectively, R⁴ and R⁶ together are

Steps a) and b) can be performed at moderate temperatures, for example at temperatures below 100° C. In addition, the steps a) and b) can be performed in an aqueous solvent such as water, and in a so-called “one pot reaction”.

EXAMPLES Example 1

Preparation of Compound 1a

20 ml 1M NaOH was added to a suspension of compound 2a (4.00 mmol) in 20 ml water and the mixture was stirred to obtain a limpid solution. Bromine (1.0 ml, 3.11 g) was added in one portion and the reaction mixture was stirred at 90-95° C. for 24 h. The precipitate was filtered and dried. The crude solid was extracted with dichloromethane. Organic solvent was evaporated to dryness and compound 1a was purified by column chromatography using hexane as eluent on silica. Yield 180 mg (10%). FD-Mass: calc.: 443.75 found: 444.0. ¹H-NMR (δ(ppm), CD₂Cl₂): 7.66 (s, 4H, CH); ¹³C-NMR (δ(ppm), CD₂Cl₂): 120.54 (4C, CBr); 130.49 (2C, C); 135.91 (4C, CH).

Example 2

Preparation of Compound 1b

10 ml 1M NaOH was added to a suspension of compound 2b (2.00 mmol) in 20 ml water and the mixture was stirred at 55° C. for 30 min. Bromine (1.0 ml) was added and reaction mixture was stirred for 24 h. The precipitate was filtered and dried. Crude compound 1b was purified by sublimation (1.27 g; 90%) or recrystallization from 1,2-dichlorobenzene (1.17 g; 83%). FD-Mass: calc.: 705.67 found: 706.0. MALDI-TOF: calc.: 705.67 found: 705.75. Elemental analysis: calc.: % C 34.04; % H 0.57; found: % C 34.23; % H 0.70. ¹H-NMR (δ(ppm), 1,2-dichlorobenzene-d₄): 7.80 (s, 4H).

Example 3

Preparation of Compound 1C

10 ml 1M NaOH was added to a suspension of compound 2c (1.42 g, 2.00 mmol) in 30 ml water and the mixture was stirred at 55° C. for 30 min. Bromine (1.0 ml) was added and reaction mixture was stirred for 24 h. The precipitate was filtered and dried (1.70 g, 96%). The crude compound 1c was purified by recrystallization from 1,2-dichlorobenzene (1.47 g; 83%). FD-Mass: calc.: 883.48 found: 883.7. Elemental analysis: calc.: % C 27.19; % H 0.46; found: % C 27.34; % H 0.53. ¹H-NMR (δ(ppm), 1,2-dichlorobenzene-d₄): 7.96 (s, 4H).

Example 4

Preparation of Compound 1d

After adding 3 ml 1M NaOH to a solution of compound 2d (0.50 mmol) in 10 ml water THF was added to obtain a clear solution. Bromine (0.40 ml) was added in one portion and the reaction mixture was stirred at room temperature for 0.5 to 1 h (TLC monitoring). A Solution of Na₂SO₃ (1 g in 10 ml water) was added and stirred for 20 min. Compound 1d was extracted with dichloromethane and purified by column chromatography using hexane as eluent on silica. Yield 5-30 mg (1-6%). ¹H-NMR (δ(ppm), CD₂Cl₂): 0.67 (s, 36H, CH₃); 1.27 (s, 12H, CH₃); 1.28 (s, 12H, CH₃); 1.65 (s, 8H, CH₂); 6.72 (d, 8H, ³J_(HH)=8.7 Hz); 7.19 (d, 8H, ³J_(HH)=8.7 Hz); 7.32 (s, 4H). FD-Mass: calc.: 1385.13; found: 1385.9.

Example 5

Preparation of Compound 2e

1M NaOH (22 ml) was added to a mixture of compound 2b (2.65 g, 5.00 mmol) and 18 ml water under argon. The mixture was stirred at 70° C. for 30 min and 1 ml Aliquat 336 (Stark' catalyst) was added and stirred additional 10 min at the same temperature. 1-lodoheptane was added and the reaction mixture was refluxed for 2 h. After cooling down to room temperature, the mixture was extracted with dichloromethane. The solvent was removed under vacuum and crude compound 2e was purified by column chromatography (silica gel, petroleum ether/dichloromethane). Yield 4.315 g (90%) as orange oil. FD-Mass: calc.: 958.87; found: 959.7. ¹H-NMR (δ(ppm), CDCl₃): 0.82 (t, 12H, CH_(3,) ³J_(HH)=6.7 Hz); 1.18-1.43 (m, 32H, CH₂); 1.74 (p, 8H, ³J_(HH)=6.9 Hz, CH₂); 4.21-4.34 (m, 8H, CH₂O); 8.01 (s, 4H, CH-perylene). ¹³C-NMR (δ(ppm), CDCl₃): 14.20 (4C, CH₃); 22.73 (4C, CH₂); 26.06 (4C, CH₂); 28.66 (4C, CH₂); 29.11 (4C, CH₂); 31.84 (4C, CH₂); 66.48 (4C, CH₂O); 123.24 (2C); 127.32 (4C); 130.90 (4C); 132.12 (4C); 133.67 (4C); 134.06 (2C); 167.11 (4C, CO). Elemental analysis calcd (%) for C₅₂H₆₄Cl₄O₈: C 65.13, H 6.73; found: C 65.17, H 6.87.

Example 6

Preparation of Compound 2f

Pd(PPh₃)₄ (780 mg, 0.67 mmol) and Bu₃SnSSnBu₃ (3.67 g, 6.00 mmol) were added to a solution of compound 2e (2.60 g, 2.71 mmol) in 100 ml toluene under argon. The mixture was stirred and refluxed for 24 h. The solvent was removed under vacuum and the crude compound 2f was washed with methanol and purified by column chromatography (silica gel, petroleum ether/ethyl acetate). Yield 1.58 g (66%). ¹H-NMR (δ(ppm), CDCl₃): 0.83 (t, 12H, CH_(3,) ³J_(HH)=6.9 Hz); 1.26-1.48 (m, 32H, CH₂); 1.83 (p, 8H, ³J_(HH)=6.9 Hz, CH₂); 4.42 (t, 8H, CH₂O, ³J_(HH)=6.9 Hz); 8.74 (s, 4H, CH-perylene). ¹³C-NMR (δ(ppm), CDCl₃): 14.22 (4C, CH₃); 22.78 (4C, CH₂); 26.26 (4C, CH₂); 28.91 (4C, CH₂); 29.24 (4C, CH₂); 31.92 (4C, CH₂); 66.22 (4C, CH₂O); 120.98 (2C); 121.54 (2C); 125.31 (4C); 129.60 (4C); 131.13 (4C); 136.83 (4C); 168.61 (4C, CO). Elemental analysis calcd (%) for C₅₂H₆₄O₈S₂: C 70.88, H 7.32; S 7.28 found: C 70.85, H 76.48, S 7.22.

Example 7

Preparation of Compound 2g

KOH (2.25 g, 34 mmol) and 5 ml water were added to a solution of compound 2f (1.5 g, 1.70 mmol) in 100 ml 2-propanol. The reaction mixture was refluxed overnight. After cooling the reaction mixture was poured onto ice/10% hydrochloric acid. The precipitate was filtered, washed with water and methanol and dried. The solid was suspended in acetic acid (50 ml) and stirred at 70° C. for 5 h. The acetic acid was removed under vacuum. The crude compound 2g was used without further purification. Yield 0.75 g (98%). FD-Mass: calc.: 452.41; found: 453.2

Example 8

Preparation of Compound 1e

4.5 ml 1M NaOH was added to a suspension of compound 2g (0.455 g, 1.00 mmol) in 20 ml water and the mixture was stirred at 30° C. for 20 min. Bromine (0.21 ml, 4.1 mmol) was added and the reaction mixture was stirred for 10 min at 30° C. The precipitate was filtered, washed with water and dried. The crude compound 1e was suspended in THF (20 ml) and filtered, washed and dried (0.56 g; 89%). MALDI-TOF: calc.: 627.99 found: 627.8 Elemental analysis calcd (%) for C₂₀H₄BraS₂: C 38.25, H 0.64; S 10.21 found: C 37.95, H 1.39, S 9.65.

Example 9

Preparation of Compound 3a

A suspension of 3,4,9,10-tetrabromo-1,6,7,12-tetrachloroperylene (0.71 g, 1.00 mmol) and sulfur (0.26 g, 8.0 mmol) in 40 ml NMP was stirred at 190° C. for 3 h. After cooling down to room temperature the reaction mixture was poured into water. The precipitate was filtered, washed with water and dried. The crude compound 3a was purified by column chromatography using dichloromethane as eluent on silica (0.50 g, 97%). FD-Mass: calc.: 514.32; found: 514.1. ¹H-NMR (δ(ppm), DMSO-d₆): 7.72 (s, 4H).

Example 10

Preparation of Compound 3b

A mixture of compound 1b (706 mg, 1 mmol), 4-(2,4,4-trimethylpentan-2-yl)phenol (1240 mg, 6 mmol) and K₂CO₃ (830 mg, 6 mmol) in 30 ml NMP was stirred at 120° C. for 5 h. The mixture was cooled down to room temperature and dichloromethane (100 ml) was added. The solution was washed several times with water, dried and evaporated. Crude compound 3b was purified by column chromatography using hexane/dichloromethane as eluent on silica. Yield 890 mg (74%). ¹H-NMR (δ(ppm), CD₂Cl₂): 0.66 (s, 36H, CH₃); 1.27 (s, 24H, CH₃); 1.65 (s, 8H, CH₂); 6.72 (d, 8H, ³J_(HH)=8.7 Hz); 6.88 (s, 4H); 7.24 (d, 8H, ³J_(HH)=8.8 Hz). ¹³C-NMR (δ(ppm), CD₂Cl₂): 31.98 (4C, CH₃); 32.01 (4C, CH₃); 32.15 (12C, CH₃); 32.83 (4C, CH₂); 38.77 (4C); 57.47 (4C); 116.29 (2C); 117.98 (4C); 118.61 (8C, CH); 121.30 (4C); 128.20 (8C, CH); 133.66 (4C); 137.32 (2C); 146.44 (4C, CH); 154.01 (4C); 154.98 (4C). FD-Mass: calc.: 1207.32; found: 1208.1.

Example 11 Preparation of Compound 3c

4.40 ml of solution of n-BuLi (1.6 M, 7 mmol) was added to a suspension of compound 1b (1 mmol, 706 mg) in 20 ml dry THF at −78° C. The reaction mixture was stirred at −78° C. for 1 h and TMSCl (0.90 ml, 7 mmol) was added dropwise to the solution. The mixture was allowed to warm gradually to room temperature and stirred additional 2 h. Methanol (1 ml) was added and the solvents were evaporated. The crude compound 3c was purified by column chromatography using hexane as eluent on silica and additional recrystallization from methanol. Yield 325 mg (48%). ¹H-NMR (δ(ppm), CDCl₃): 0.52 (s, 18H, CH₃); 0.54 (s, 18H, CH₃); 7.68 (s, 2H); 8.18 (s, 2H). ¹³C-NMR (δ(ppm), CD₂Cl₂): 0.07 (6C, CH₃); 0.28 (6C, CH₃); 125.59 (2C); 125.84 (2C); 131.39 (2C); 132.67 (2C); 134.52 (2C); 134.93 (2C); 135.58 (2C); 138.28 (2C); 138.76 (2C); 140.26 (2C).

Example 12

Preparation of Compound 3d

A suspension of compound 1b (2.11 g, 3.00 mmol) and CuCN (5.40 g, 60 mmol) in 50 ml DMF was stirred at 130° C. for 2 h. After cooling down to room temperature the reaction mixture was poured in water. The precipitate was filtered, dried and dissolved in 600 ml dichloromethane. 20 g of silica was added to the solution and evaporated to dryness. Crude compound 3d was purified by column chromatography using dichloromethane as eluent on silica. (1.03 g, 70%). FD-Mass: calc.: 490.13; found: 489.7. ¹H-NMR (δ(ppm), C₂D₂Cl₄): 8.21 (s, 4H, CH). 

1. A process for the preparation of compounds of formula

wherein n is 0 or 1, R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰, Si(R³⁰¹)₃, NHR³⁰², NR³⁰³R³⁰⁴, SR³⁰⁵ and R³⁰⁶, wherein R³⁰⁰, R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵ and R³⁰⁶ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³ and C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷, wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R¹¹ and R¹² together are selected from the group consisting of

wherein L¹ and L² are C₁₋₆-alkylene, C₆₋₁₄-arylene, or C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene, R²⁵ is H, C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰¹⁰R³⁰¹¹, O—R³⁰¹² and S—R³⁰¹³, and C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR₃₀₁₄R₃₀₁₅, O—R³⁰¹⁶ and S—R³⁰¹⁷, wherein R³⁰¹⁰, R³⁰¹¹, R³⁰¹², R³⁰¹³, R³⁰¹⁴, R³⁰¹⁵, R³⁰¹⁶ and R³⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene, and R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴, wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ and C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen, wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

which process comprises the step of treating a compound of formula

wherein n has the meaning as depicted for formula (3), R⁹ and R¹⁰ are the same or different and are COOH or COOR²⁰⁰, wherein R₂₀₀ is C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR²⁰⁰⁰R²⁰⁰¹, O—R²⁰⁰² and S—R²⁰⁰³, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR²⁰⁰⁴R²⁰⁰⁵, O—R²⁰⁰⁶ and S—R²⁰⁰⁷, wherein R²⁰⁰⁰, R²⁰⁰¹, R²⁰⁰² and R²⁰⁰³, R²⁰⁰⁴, R²⁰⁰⁵, R²⁰⁰⁶ and R²⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R⁹ and R¹⁰ together are

and R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R²⁰⁰, OR²⁰¹, SR²⁰², OC(O)R²⁰³ and C(O)OR²⁰⁴, wherein R²⁰⁰, R²⁰¹, R²⁰², R²⁰³ and R²⁰⁴ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen, wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R³ and R⁵, respectively, R⁴ and R⁶ together are

a) with MOH, wherein M is an alkali metal, N(R⁴⁰⁰R⁴⁰¹R⁴⁰²R⁴⁰³), P(R⁴⁰⁰R⁴⁰¹R⁴⁰²R⁴⁰³) or hexa(C₁₋₁₀-alkyl)guanidinium, wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰² and R⁴⁰³ are the same or different and are selected from the group consisting of H, C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl and C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with phenyl, C₆₋₁₄-aryl may be substituted with C₁₋₁₀-alkyl, and b) an X-donor, wherein X is Cl, Br or I, in order to obtain a compound of formula

wherein X has the meaning as depicted for the X-donor, n has the meaning as depicted for formula (3), and R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ have the meaning as depicted for formula (2).
 2. The process of claim 1, wherein R⁹ and R¹⁰ together are


3. The process of claim 1, wherein n is
 1. 4. The process of claim 1, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, Cl, Br, I, CN and OR²⁰¹, wherein R²⁰¹ is C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂CN and halogen, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR²⁰¹⁴R²⁰¹³, O—R²⁰¹⁶S—R²⁰¹⁷, NO₂, CN and halogen, wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R³ and R⁵, respectively, R⁴ and R⁶ together are


5. The process of claim 1, wherein R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, Cl, Br, I, CN and OR³¹¹, wherein R³¹¹ is C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂.₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen, wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are


6. The process of claim 1, wherein R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃, wherein R³⁰⁰ and R³⁰¹ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³ and C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷, wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R¹¹ and R¹² together are

wherein L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene.
 7. The process of claim 1, wherein R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃, wherein R³⁰⁰ and R³⁰¹ are C₁₋₂₀-alkyl or C₆₋₁₄-aryl, wherein C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷, wherein R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R¹¹ and R¹² together are


8. Compounds of formula

wherein X is Cl, Br or I, n is 0 or 1, and R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R²⁰⁰, R²⁰¹, SR²⁰², OC(O)_(R) ²⁰³ and C(O)OR²⁰⁴, wherein R²⁰⁰, R²⁰¹, R²⁰², R²⁰³ and R²⁰⁴ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³NO₂, CN and halogen, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen, wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R³ and R⁵, respectively, R⁴ and R⁶ together are

with the proviso that if n is 0 and X is Cl, R¹ , R², R³ and R⁴ are not H, Cl, CN, R₂₀₀ or C(O)OR²⁰⁴, wherein R₂₀₀ and R²⁰⁴ are C₁₋₂₀-alkyl, that if n is 0 and X is Br, R¹, R², R³ and R⁴ are not H, Br or R²⁰⁰, wherein R₂₀₀ is C₁₋₂₀-alkyl, that if n is 1 and X is Cl or Br, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are not H.
 9. The compounds of claim 8, wherein n is
 1. 10. The compounds of claim 9, wherein R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ are the same or different and are selected from the group consisting of F, Cl, Br, I, CN, R²⁰⁰, OR²⁰¹, SR²⁰², OC(O)R²⁰³ and C(O)OR²⁰⁴, wherein R²⁰⁰, R²⁰¹, R²⁰², R²⁰³ and R²⁰⁴ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂, CN and halogen, wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R³ and R⁵, respectively, R⁴ and R⁶ together are


11. The compounds of claim 10, wherein R¹, R², R⁷ and R⁸ are H, and R³, R⁴, R⁵ and R⁶ are the same or different and are selected from the group consisting of Cl, Br, I, CN and OR²⁰¹, wherein R²⁰¹ is C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR²⁰¹⁰R²⁰¹¹, O—R²⁰¹², S—R²⁰¹³, NO₂, CN and halogen, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR²⁰¹⁴R²⁰¹⁵, O—R²⁰¹⁶, S—R²⁰¹⁷, NO₂CN and halogen, wherein R²⁰¹⁰, R²⁰¹¹, R²⁰¹², R²⁰¹³, R²⁰¹⁴, R²⁰¹⁵, R²⁰¹⁶ and R²⁰¹⁷ are the same or different and are C₁₋₁1₃-alkyl or phenyl, or R³ and R⁵, respectively, R⁴ and R⁶ together are


12. Compounds of formula

wherein n is 0 or 1, R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰, Si(R³⁰¹)₃, NHR³⁰², NR³⁰³R³⁰⁴, SR³⁰⁵ and R³⁰⁶ wherein R³⁰⁰, R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, SR³⁰⁵ and R³⁰⁶ and R³⁰⁶ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³ and C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷, wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R¹ and R¹² together are selected from the group consisting of

wherein L¹ and L² are C₁₋₆-alkylene, C₆₋₁₄-arylene, or C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene, R²⁵ is H, C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰¹⁰R³⁰¹¹, O—R³⁰¹² and S—R³⁰¹³, and C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰¹⁴R³⁰¹⁵, O—R³⁰¹⁶ and S—R³⁰¹⁷, wherein R³⁰¹⁰, R³⁰¹¹, R³⁰¹², R³⁰¹³, R³⁰¹⁴, R³⁰¹⁵, R³⁰¹⁶ and R³⁰¹⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene, and R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴, wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen, wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are

with the proviso that if n is 0, R¹¹ and R¹² are both CN, then R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are not all H, and that if n is 1, R¹¹ and R¹² are both CN or phenyl, and R¹⁵, R¹⁶ R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are H, then R¹⁷ and R²⁰ are not Br.
 13. The compounds of any of claim 12, wherein R¹¹ and R¹² are the same and are selected from the group consisting of CN, OR³⁰⁰ and Si(R³⁰¹)₃, wherein R³⁰⁰ and R³⁰¹ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰⁰⁰R³⁰⁰¹, O—R³⁰⁰² and S—R³⁰⁰³ and C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰⁰⁴R³⁰⁰⁵, O—R³⁰⁰⁶ and S—R³⁰⁰⁷, wherein R³⁰⁰⁰, R³⁰⁰¹, R³⁰⁰², R³⁰⁰³, R³⁰⁰⁴, R³⁰⁰⁵, R³⁰⁰⁶ and R³⁰⁰⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R¹¹ and R¹² together are

wherein L³ is a direct bond, C₁₋₆-alkylene, C₆₋₁₄-arylene, or C₁₋₆-alkylene-C₆₋₁₄-arylene-C₁₋₆-alkylene.
 14. The compounds of claim 12, wherein R¹¹ and R¹² together are


15. The compounds of claim 12, wherein n is
 1. 16. The compounds of of claim 15, wherein R¹⁵, R¹⁶, R²¹, R²² are H, and R¹⁷, R¹⁸, R¹⁹ and R²⁰, are the same or different and are selected from the group consisting of H, Cl, Br, I, CN, R³¹⁰, OR³¹¹, SR³¹², OC(O)R³¹³ and C(O)OR³¹⁴, wherein R³¹⁰, R³¹¹, R³¹², R³¹³ and R³¹⁴ are C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₈-cycloalkyl or C₆₋₁₄-aryl, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl and C₅₋₈-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR³⁰²⁰R³⁰²¹, O—R³⁰²², S—R³⁰²³, NO₂, CN and halogen, C₆₋₁₄-aryl may be substituted with one or more substituents selected from the group consisting of C₁₋₁₀-alkyl, NR³⁰²⁴R³⁰²⁵, O—R³⁰²⁶, S—R³⁰²⁷, NO₂, CN and halogen, wherein R³⁰²⁰, R³⁰²¹, R³⁰²², R³⁰²³, R³⁰²⁴, R³⁰²⁵, R³⁰²⁶ and R³⁰²⁷ are the same or different and are C₁₋₁₀-alkyl or phenyl, or R¹⁷ and R¹⁹, respectively, R¹⁸ and R²⁰ together are


17. Use of the compounds of formula (3) of claim 12 in electronic devices.
 18. Use of the compounds of formula (3) of claim 12 as dye. 